Metal free acid dyes, process for the production thereof and their use

ABSTRACT

The present invention relates to dyes of formula (1) 
     
       
         
         
             
             
         
       
     
     a process for preparing them and their use for dyeing and printing hydroxyl- and/or carboxamido-containing materials.

The present invention relates to the technical field of dyestuffs fordyeing and printing of hydroxyl- and/or carboxamido containing material.

Disazo compounds comprising a triazine moiety are known and can be usedas colorants in different applications, see for example GB 2,036,780,U.S. Pat. No. 3,945,990, U.S. Pat. No. 5,006,128 and U.S. Pat. No.5,519,121.

In the context of the dyeing and printing of hydroxyl- and/orcarboxamido-containing material the known dyes have a number oftechnical disadvantages, which need to be overcome.

Surprisingly, it has now been found that the dyes of the formula (1) asdescribed below show highly advantageous properties over the known dyes.These include high tinctorial strength with high brilliancy as well ashigh fastness properties such as wash, contact and light fastness on thematerials mentioned above, on blends containing them as well as onmicrofibres. Most importantly, dyes of formula (1) are metal free andprovide dyeings that are levelled.

The present invention refers to a Dye of formula (1)

wherein independent from each other

G is a rest of formula (i) or (ii)

R¹, R², R³ and R⁴ is

-   -   hydrogen,    -   (C₁-C₁₂)-alkyl,    -   (C₂-C₆)-alkenyl,    -   (C₃-C₈)-cycloalkyl or    -   aryl-(C₁-C₁₂)-alkyl,    -   with the alkyl chain being linear or branched, and optionally        being interrupted by one or more heteroatoms and/or substituted        by one or more substituents selected from the group consisting        of hydroxy, carboxy, SO₃M, halogen, cyano, nitro, acyl,        trifluoromethyl, acyloxy, aryloyloxy and carbamoyl,

R⁵ and R⁶ is

-   -   hydrogen,    -   (C₁-C₁₂)-alkyl,    -   substituted (C₁-C₁₂)-alkyl with the substituents being selected        from the group consisting of hydroxy, carboxy, SO₃M, halogen,        cyano, nitro, acyl, trifluoromethyl, acyloxy, aryloyloxy and        carbamoyl,    -   (C₃-C₈)-cycloalkyl,    -   a group of formula (iii)

-   -   -   wherein        -   R²⁶ and R²⁷ is        -   hydrogen,        -   (C₁-C₁₂)-alkyl,        -   (C₁-C₁₂)-alkyl substituted by hydroxy, (C₁-C₁₂)-alkoxy,            trifluoromethyl, cyano, nitro, halogen, —NHCO(C₁-C₆)-alkyl            or —NHSO₂(C₁-C₆)-alkyl, CONH₂ or SO₂NH₂,        -   R⁴¹ is hydrogen or (C₁-C₆)-alkyl,        -   n is 0,1 or 2,        -   p is 0 or 1 to 6, or

    -   (C₁-C₁₂)-alkyl, whereby the alkyl chain can be interrupted by        one or more heteroatoms,

R⁷ and R⁸ is

-   -   hydrogen,    -   (C₁-C₆)-alkyl or    -   phenyl,

R⁹ and R¹⁰ is hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkoxy, trifluoromethyl,hydroxy, cyano, nitro, halogen, —NHCHO, —NHCO(C₁-C₆)-alkyl, —NHCOaryl,—NHSO₂(C₁-C₆)-alkyl or —NHSO₂aryl,

D¹ and D² is a rest of a phenyl-, naphthyl- or heterocyclic-derivative,which comprises at least one group —SO₃M, wherein M is hydrogen, analkali metal, ammonium, substituted or unsubstituted tetra(C₁-C₁₂)-alkylammonium or one equivalent of an alkali earth metal.

(C₁-C₁₂)-alkyl groups appearing in this application may bestraight-chain or branched and are for example methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl,isopentyl, methylbutyl and n-hexyl. The same logic applies to alkoxygroups which for example are methoxy and ethoxy.

Rests of phenyl-, naphtyl- or heterocyclic-derivatives are rests, whichare based on phenyl-, naphtyl- or heterocyclic structures. Thesestructures may be substituted or unsubstituted in general. In thepresent invention these structures carry at least one group —SO₃M, whenthey are D¹ or D² as outlined above. Preferred phenyl-, naphtyl- andheterocyclic structures are mentioned below.

Cycloalkyl groups are preferably (C₃-C₈)-cycloalkyl and especiallypreferably cyclopentyl and cyclohexyl. The term cyloalkyl comprises forthe purpose of the present application substituted cycloalkyl groups andunsaturated cycloalkyl groups as well. A preferred group of this type iscyclopentenyl or cyclohexenyl. Preferred substituents are alkyl,hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino,monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino,bis-(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl,sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl andacyloxy.

(C₂-C₆)-alkenyl groups may be straight-chain or branched and are forexample vinyl and allyl. The term alkenyl comprises for the purpose ofthe present application alkynyl groups as well, for example ethynyl andpropargyl.

Heteroaryl groups or a heteroaryl rest appearing in this application arepreferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole,benzimidazole, benzotriazole, imidazole, pyrazole, 1,2,4-thiadiazole,1,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole,benzothiazole, benzoisothiazole, 1,3,4-thiadiazole, furane, oxazole,1,2,4-oxadiazole, 1,3,4-oxadiazole, benzoxazole or isoxazole. The termsheteroaryl comprises the above groups in unsubstituted as well as insubstituted form. Preferred substituents are alkyl, hydroxyalkyl,halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino,monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino,bis(hydroxylalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl,sulfamoyl, acylamino, ureido, amino-sulfonylamino, alkoxycarbonyl andacyloxy.

Heterocycloalkyl groups are preferably pyrrolidine, piperidine,morpholine, tetra-hydrofuran or piperazine. The term heterocycloalkylcomprises the above groups in unsubstituted as well as in substitutedform. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl,alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkyl-amino,dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino,monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino,aminocarbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Aryl or aryl rest appearing in this application is in particular phenylor naphthyl. The terms phenyl and naphthyl comprise unsubstituted aswell as substituted phenyl and naphthyl. Preferred substituents arealkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl,alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino,dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino,monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino,ureido, aminosulfonylamino, alkoxycarbonyl or acyloxy.

Halogen is preferably chlorine, bromine or fluorine.

There also exist preferred structures. Thus a Dye as described above,wherein independent from each other

R¹ to R⁴ are identical and are hydrogen, (C₁-C₄)-alkyl or (C₁-C₆)-alkylsubstituted by hydroxyl, cyano or alkenyl,

R⁵ and R⁶ are identical and are

-   -   hydrogen,    -   (C₁-C₆)-alkyl,    -   (C₁-C₆)-alkyl substituted by hydroxy,    -   (C₃-C₈)-cycloalkyl or (C₁-C₆)-alkyl substituted by —SO₃M or a        group of formula (iii) as defined in claim 1, wherein each R²⁶        and R²⁷ independent from each other is        -   hydrogen,        -   (C₁-C₆)-alkyl,        -   (C₁-C₆)-alkyl substituted by hydroxy,        -   (C₁-C₆)-alkoxy, trifluoromethyl, hydroxy, cyano, halogen,        -   n is 0 or 1,        -   p is 0 or 1 to 4,

R⁷ and R⁸ are identical and are hydrogen, methyl or ethyl and

R⁹ and R¹⁰ are identical and are hydrogen, methyl, ethyl, halogen,trifluoromethyl, methoxy or ethoxy is preferred.

“Independent from each other” in this context means that a selection ofe.g. R⁷ and R⁸ being identical and being e.g. hydrogen has no influenceon what is selected for e.g. R⁹ and R¹⁰. R⁹ and R¹⁰ in this case may bedifferent to each other or identical. A dye where R¹ to R⁴ are identicaland R⁵ and R⁶ are identical and R⁷ and R⁸ are identical and R⁹ and R¹⁰are identical is preferred.

Even more preferred is a Dye as described above, having formula (1a),(1a¹), (1a²) or (1a³)

wherein

R^(5a) and R^(6a) are hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkyl substitutedby hydroxy, (C₃-C₈)-cycloalkyl or (C₁-C₆)-alkyl substituted by SO₃M,

R^(9a) and R^(10a) are identical and are hydrogen or methoxy,

each of R^(26a), R^(27a), R^(26b) and R^(27b) is hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, trifluoromethyl, cyano, nitro or halogen,

R^(43a) and R^(43b) is hydrogen or (C₁-C₄) alkyl,

s is 0 or 1 to 6 and

D¹ and D² are as defined above,

Still more preferred is a Dye as described above, in which independentfrom each other D¹ and D² is selected from the group consisting ofgroups of formula (I) to (XIV):

-   -   wherein    -   R¹¹ and R³⁰ independent of each other is hydrogen,        (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, trifluoromethyl, cyano, nitro,        NHC(O)R³¹, CONH₂, S(O)₂R³² or halogen,        -   R³¹ and R³² is hydrogen, (C₁-C₄)-alkyl or (C₁-C₄)-alkyl            substituted by hydroxyl,    -   M is hydrogen, an alkali metal, ammonium or one equivalent of an        alkali earth metal,

-   -   wherein    -   R¹² is hydrogen or (C₁-C₄)-alkyl,    -   n is 0 or 1 and    -   M is defined as given above,

-   -   wherein    -   R¹³ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, cyano, nitro,        CONH₂ or halogen and    -   M is defined as given above,

-   -   wherein    -   R¹⁴ is hydrogen, cyano, CONH₂, C(O)R³³ or COOR³⁴,    -   R³³ is hydrogen or (C₁-C₄)-alkyl,    -   R³⁴ is hydrogen or (C₁-C₄)-alkyl,    -   R¹⁵ is hydrogen, -CHO or a group of formula (a) or (c)

-   -   wherein    -   R¹⁶ , R³⁵ and R³⁶ independent of each other is hydrogen,        halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, SO₃M or —CONH₂,    -   m is 0 or 1 and    -   M is defined as given above,

-   -   wherein    -   M is defined as given above,

-   -   wherein    -   R¹⁷ is —SO₃M, —CHO, —CH═C(CN)₂, a group of formula (a) as        defined above or a group of formula (b) or (d)

-   -   wherein    -   R³⁷, R³⁸ and R³⁹ independent of each other is hydrogen, halogen,        (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, SO₃M or —CONH₂,    -   R¹⁸ is —SO₃M, (C₁-C₄)-alkyl, sulfophenyl (C₁-C₄)-alkylamino,        (C₁-C₁₂)-alkylamino, (C₅-C₆)-cycloalkylamino, morpholino or        piperidino and    -   M is defined as given above,

-   -   wherein    -   R¹⁹ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro,        NHC(O)R⁴⁰, NHSO₂R⁴⁷ or halogen,    -   R⁴⁰ is hydrogen or (C₁-C₆) alkyl,    -   R⁴⁷ is (C₁-C₆)-alkyl,

-   -   wherein    -   R²⁰ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, cyano, nitro,        CONH₂ or halogen,

-   -   wherein    -   R²¹ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, cyano,        nitro or CONH₂ and    -   E is sulphur or oxygen,

-   -   wherein    -   R²² and R²³ independent of each other is hydrogen,        (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, cyano or CONH₂ and    -   U is methylene or C═O,

-   -   wherein    -   R²⁴ and R²⁵ independent of each other is hydrogen,        (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, cyano, nitro,        trifluoromethyl or CONH₂,

-   -   wherein    -   R⁴⁴ and R⁴⁵ independent of each other is hydrogen,        (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, cyano, nitro,        trifluoromethyl, CONH₂ or SO₃M,

-   -   wherein    -   R⁴⁶ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, cyano,        nitro, trifluoromethyl, CONH₂ or SO₃M,

and

-   -   wherein    -   R⁴⁸ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro,        NHC(O)R⁴⁹, NHSO₂R⁵⁰ or halogen,    -   R⁴⁹ is hydrogen or (C₁-C₆)-alkyl,    -   R⁵⁰ is (C₁-C₆)-alkyl;    -   and    -   M is defined as given above.

M is preferably hydrogen, lithium, sodium or potassium,

There exist groups of preferred dyes. One preferred group consists ofdyes as described above, wherein D¹ and D² are selected from the samegroup (I) to (XIV). Another preferred group consists of dyes asdescribed above, wherein D¹ and D² are selected from different groups(I) to (XIV). Most preferred, however, is a Dye as described above,wherein D¹ and D² are identical.

The most preferred dyes of the present invention are the dyes of theformulae (1aa) to (1an), (1a¹a) to (1a¹n), (1a²a) to (1a²n) and (1a³a)to (1a³n)

wherein R⁴, R⁵, R^(9a), R^(10a), R¹¹ to R¹⁵, R¹⁷, R¹⁸, R²² to R²⁵,R^(26a), R^(27a), R³⁰, R^(43a), R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁸, E, T, U, M, n, s andm are defined as given above.

Examples of preferred embodiments of this invention are the dyes from1-1 to 1-288 (Table 1) and mixtures thereof.

TABLE 1 Example Structure 1-1 

1-2 

1-3 

1-4 

1-5 

1-6 

1-7 

1-8 

1-9 

1-10 

1-11 

1-12 

1-13 

1-14 

1-15 

1-16 

1-17 

1-18 

1-19 

1-20 

1-21 

1-22 

1-23 

1-24 

1-25 

1-26 

1-27 

1-28 

1-29 

1-30 

1-31 

1-32 

1-33 

1-34 

1-35 

1-36 

1-37 

1-38 

1-39 

1-40 

1-41 

1-42 

1-43 

1-44 

1-45 

1-46 

1-47 

1-48 

1-49 

1-50 

1-51 

1-52 

1-53 

1-54 

1-55 

1-56 

1-57 

1-58 

1-59 

1-60 

1-61 

1-62 

1-63 

1-64 

1-65 

1-66 

1-67 

1-68 

1-69 

1-70 

1-71 

1-72 

1-73 

1-74 

1-75 

1-76 

1-77 

1-78 

1-79 

1-80 

1-81 

1-82 

1-83 

1-84 

1-85 

1-86 

1-87 

1-88 

1-89 

1-90 

1-91 

1-92 

1-93 

1-94 

1-95 

1-96 

1-97 

1-98 

1-99 

1-100

1-101

1-102

1-103

1-104

1-105

1-106

1-107

1-108

1-109

1-110

1-111

1-112

1-113

1-114

1-115

1-116

1-117

1-118

1-119

1-120

1-121

1-122

1-123

1-124

1-125

1-126

1-127

1-128

1-129

1-130

1-131

1-132

1-133

1-134

1-135

1-136

1-137

1-138

1-139

1-140

1-141

1-142

1-143

1-144

1-145

1-146

1-147

1-148

1-149

1-150

1-151

1-152

1-153

1-154

1-155

1-156

1-157

1-158

1-159

1-160

1-161

1-162

1-163

1-164

1-165

1-166

1-167

1-168

1-169

1-170

1-171

1-172

1-173

1-174

1-175

1-176

1-177

1-178

1-179

1-180

1-181

1-182

1-183

1-184

1-185

1-186

1-187

1-188

1-189

1-190

1-191

1-192

1-193

1-194

1-195

1-196

1-197

1-198

1-199

1-200

1-201

1-202

1-203

1-204

1-205

1-206

1-207

1-208

1-209

1-210

1-211

1-212

1-213

1-214

1-215

1-216

1-217

1-218

1-219

1-220

1-221

1-222

1-223

1-224

1-225

1-226

1-227

1-228

1-229

1-230

1-231

1-232

1-233

1-234

1-235

1-236

1-237

1-238

1-239

1-240

1-241

1-242

1-243

1-244

1-245

1-246

1-247

1-248

1-249

1-250

1-251

1-252

1-253

1-254

1-255

1-256

1-257

1-258

1-259

1-260

1-261

1-262

1-263

1-264

1-265

1-266

1-267

1-268

1-269

1-270

1-271

1-272

1-273

1-274

1-275

1-276

1-277

1-278

1-279

1-280

1-281

1-282

1-283

1-284

1-285

1-286

1-287

1-288

The dyes of the present invention can be used alone or as a mixture withother dyes according to the present invention and/or other substances.

Thus a chemical composition comprising one or more dye(s) as describedabove is also an aspect of the present invention.

A chemical composition consisting of two or more dyes as described aboveforms another preferred aspect of the present invention.

Also an aqueous solution for dying comprising one or more dye(s) asdescribed above forms an aspect of the present invention.

A process for the production of a dye according to the invention,comprising

a) diazotization of compounds of formulae (2) and (3)

D¹-NH₂   (2)

D²-NH₂   (3),

-   -   wherein D and D² are defined as given in claim 1,

b) reacting the products obtained in step a) with a compound of formula(4)

-   -   wherein R¹ to R¹⁰ and G are defined as given above is another        aspect of the present invention.

The diazotization of the compounds of formulae (2) and (3) can beperformed by means of diazotization methods that are known to a personskilled in the art, preferably by using sodium nitrite ornitrosylsulfuric acid in acidic medium using inorganic acids such ashydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereofor organic acids such as acetic acid or propionic acid or mixturesthereof. Also mixtures of inorganic acid with organic acids can be usedadvantageously.

The coupling reaction of the diazotized compounds of formulae (2) and(3) onto the compound of formula (4) can likewise be performed by knownmethods.

The compounds of the formula (2) to (4) are known and commerciallyavailable or can be synthesised by means of common chemical reactionsknown to a person skilled in the art.

The compound of formula (4) can for example be obtained by reacting2,4,6-trichlorotriazine with the compounds of the formulae (5)-(8)

wherein R¹ to R¹⁰ are defined as given above, according to condensationreactions which are known to a person skilled in the art.

The dyes of the present invention are suitable for dyeing and printingof natural, manufactured regenerated, modified or synthetic hydroxyl-amino-, and/or carboxamido-containing fiber materials and their blendsby the application methods numerously described in the art for aciddyes.

Therefore, the present invention also is directed to a Process fordyeing or printing carboxamido- and/or hydroxyl-containing material,comprising contacting the carboxamido- and/or hydroxyl-containingmaterial with a dye as described above.

The use of a dye as described above, a chemical composition as describedabove or of an aqueous solution as described above for dying fibers, aswell as blends of such fibres selected from the group consisting of:synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 andaramid fibres, vegetable fibres, seed fibres, cotton, organic cotton,kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf,ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres,bamboo; fibres from animals, wool, organic wool, silk, cashmere wool,alpaca fiber, mohair, Angora fibre as well as fur and leather materials;manufactured, regenerated and recycled fibres, cellulosic fibres; paperfibres, cellulosic regenerated fibres, viscose rayon fibres, acetate andtriacetate fibers and Lyocell fibers forms another aspect of the presentinvention.

Still another aspect of the present invention is/are: Fiber and blendscontaining such fiber selected from the group consisting of: syntheticfiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres,vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir fromcoconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaffibres, sisal, henequen, banana; stalk fibres, bamboo; fibres fromanimals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair,Angora fibre as well as fur and leather materials; manufactured,regenerated and recycled fibres, cellulosic fibres; paper fibres,cellulosic regenerated fibres, viscose rayon fibres, acetate andtriacetate fibers, and Lyocell fibers comprising one or more dye(s) ofthe present invention either in chemically and/or physically bound form.

The above-mentioned substrates to be dyed can be present in variousforms such as but not limited to yarn, woven fabric, loop-forminglyknitted fabric or carpet. For instance in the form of sheetlikestructures, such as paper and leather, in the form of films, such asnylon films, or in the form of a bulk mass, for example composed ofpolyamide and polyurethane, in particular in the form of fibers, forexample cellulose fibers. The fibers are preferably textile fibers, forexample in the form of woven fabrics or yarns or in the form of hanks orwound packages.

The dyes of the present invention and their salts and/or mixtures can beused as a single dyeing colorant in dyeing or printing processes or canbe part of a di-, tri- or multi-component combination colorant in dyeingor in printing compositions. The di-, tri- or multi-component shadedyeings show similar fastness level as compared to dyeing performed witha single colorant component.

Dyes of the present invention and their salts or mixtures are highlycompatible with other known and/or commercially available acid dyes andthey can be used together with such dyes of related chromophores andsimilar technical performance to obtain specific hues. Similar technicalperformance includes: comparable build-up, comparable fastnessproperties and comparable exhaustion rates during dyeings.

The dyes according to the invention can be applied to the materialsmentioned, especially the fiber materials mentioned, by the applicationtechniques known for water-soluble dyes. This applies to both, dyeingand printing processes.

It applies in particular to the production of dyeings on fiber materialscomposed of wool or other natural polyamides or of synthetic polyamidesand their mixtures with other fiber material. In general, the materialto be dyed is introduced into the bath at a temperature of about 40° C.,agitated therein for some time, the dyebath is then adjusted to thedesired weakly acidic, preferably weakly acetic acid, pH and the actualdyeing is carried out at a temperature between 60 and 98° C. However,the dyeings can also be carried out at the boil or in a sealed dyeingapparatus at temperatures of up to 106° C.

Since the water solubility of the dyes according to the invention isvery good, they can also be used with advantage in customary continuousdyeing processes.

The dyes of the present invention can also be used in digital printingprocesses, in particular in digital textile printing. For this the dyesof the present invention need to be formulated in aqueous inks.

An Ink for digital textile printing, comprising a dye of the presentinvention is another aspect of the present invention.

The inks of the present invention comprise the dye of the presentinvention in amounts which preferably range from 0.1 to 50% by weight,more preferably from 0.5 to 30% by weight and most preferably from 1 to15% by weight, based on the total weight of the ink.

If desired the inks may contain further dyes used in digital printing inaddition to the one or more dyes of the present invention.

For the inks of the present invention to be used in the continuous flowprocess, a conductivity of 0.5 to 25 mS/m can be set by adding anelectrolyte. Useful electrolytes include for example lithium nitrate andpotassium nitrate. The inks of the present invention may include organicsolvents at a total level of 1 to 50% by weight and preferably 5 to 30%by weight. Suitable organic solvents are for example alcohols, forexample methanol, ethanol, 1-propanol, isopropanol, 1-butanol,tert-butanol, pentyl alcohol, polyhydric alcohols for example:1,2-ethanediol, 1,2,3-propanetriol, butanediol, 1,3-butanediol,1,4-butanediol, 1,2-propanediol, 2,3-propanediol, pentanediol,1,4-pentanediol, 1,5-pentanediol, hexanediol, D,L-1,2-hexanediol,1,6-hexanediol, 1,2,6-hexanetriol, 1,2-octanediol, polyalkylene glycols,for example: polyethylene glycol, polypropylene glycol, alkylene glycolshaving 1 to 8 alkylene groups, for example: monoethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol,thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol,dipropylene glycol, tripropylene glycol, low alkyl ethers of polyhydricalcohols, for example: ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, ethylene glycol monobutyl ether, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, diethylene glycol monohexyl ether, triethylene glycolmonomethyl ether, triethylene glycol monobutyl ether, tripropyleneglycol monomethyl ether, tetraethylene glycol monomethyl ether,tetraethylene glycol monobutyl ether, tetraethylene glycol dimethylether, propylene glycol monomethyl ether, propylene glycol monoethylether, propylene glycol monobutyl ether, tripropylene glycol isopropylether, polyalkylene glycol ethers, such as for example: polyethyleneglycol monomethyl ether, polypropylene glycol glycerol ether,polyethylene glycol tridecyl ether, polyethylene glycol nonylphenylether, amines, such as for example: methylamine, ethylamine,triethylamine, diethylamine, dimethylamine, trimethylamine,dibutylamine, diethanolamine, triethanolamine, N-acetylethanolamine,N-formylethanolamine, ethylenediamine, urea derivatives, such as forexample: urea, thiourea, N-methylurea, N,N′-epsilon dimethylurea,ethyleneurea, 1,1,3,3-tetramethylurea, amides, such as for example:dimethylformamide, dimethylacetamide, acetamide, ketones or ketoalcohols, such as for example: acetone, diacetone alcohol, cyclicethers, such as for example: tetrahydrofuran, trimethylolethane,trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol,gamma butyrolactone, epsilon-caprolactam, further sulfolane,dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethylsulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide,N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone,2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone,1-(3-hydroxypropyl)-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,1,3-dimethyl-2-imidazolinone, 1,3-bismethoxymethylimidazolidine,2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol,2-(2-butoxyethoxy)ethanol, 2-(2-propoxyethoxy)ethanol, pyridine,piperidine, butyrolactone, trimethylpropane, 1,2-dimethoxypropane,dioxane ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether,1,2-dimethoxypropane and trimethylpropane.

The inks of the present invention may further include customaryadditives, for example viscosity moderators to set viscosities in therange from 1.5 to 40.0 mPas in a temperature range from 20 to 50° C.Preferred inks have a viscosity of 1.5 to 20 mPas and particularlypreferred inks have a viscosity of 1.5 to 15 mPas.

Useful viscosity moderators include rheological additives, for example:polyvinylcaprolactam, polyvinylpyrrolidone and their copolymerspolyetherpolyol, associative thickeners, polyurea, polyurethane, sodiumalginates, modified galactomannans, polyetherurea, polyurethane,nonionic cellulose ethers.

As further additives the inks of the invention may includesurface-active substances to set surface tensions of 20 to 65 mN/m,which are adapted if necessary as a function of the process used(thermal or piezo technology). Useful surface-active substances includefor example: all surfactants, preferably nonionic surfactants,butyldiglycol, 1,2-hexanediol.

The inks of the present invention may further comprise customaryadditives, for example substances to inhibit fungal and bacterial growthin amounts from 0.01 to 1% by weight based on the total weight of theink.

The inks may be prepared in a conventional manner by mixing thecomponents in water.

The inks of the invention are particularly useful in inkjet printingprocesses for printing a wide variety of pretreated materials, such assilk, leather, wool, polyamide fibers and polyurethanes, and cellulosicfiber materials of any kind. Blend fabrics, for example blends ofcotton, silk, wool with polyester fibers or polyamide fibers cansimilarly be printed.

In contrast to conventional textile printing, where the printing inkalready contains all necessary chemicals, in digital or inkjet printingthe auxiliaries have to be applied to the textile substrate in aseparate pretreatment step.

The pretreatment of the textile substrate, for example cellulose andregenerated cellulose fibers and also silk and wool, is effected with anaqueous alkaline liquor prior to printing. In addition there is a needfor thickeners to prevent flowing of the motives when the printing inkis applied, for example sodium alginates, modified polyacrylates orhighly etherified galactomannans.

These pretreatment reagents are uniformly applied to the textilesubstrate in a defined amount using suitable applicators, for exampleusing a 2- or 3-roll pad, contactless spraying technologies, by means offoam application or using appropriately adapted inkjet technologies, andsubsequently dried.

The examples below serve to illustrate the invention. Parts andpercentages are by weight unless noted otherwise. The relationshipbetween parts by weight and parts by volume is that of the kilogram tothe liter.

EXAMPLE 1

a) 63.22 parts of hydrochloric acid (30%) were transferred into a 250 mlround bottom flask equipped with mechanical stirrer, temperaturecontroller and condenser. 50 parts of 3-(diethylamino)acetanilide (A)were added slowly. The reaction mixture was heated to 80° C. graduallywithin 1 hour. The reaction mixture was kept at 80° C. until thereaction was completed. The reaction mixture was cooled down and dilutedwith deionized water. After the pH was adjusted to slightly alkalinewith 90 parts of 30%

NaOH solution the reaction mixture was extracted with organic solvent.The organic layer was washed three times with 500 parts of deionisedwater and dried over anhydrous sodium sulfate. The organic layer wasdistilled to dryness. 35 parts of the product (B) as dark brown viscousoil were obtained. The analytic data are consistent with the assignedstructure for product (B).

b) 109 parts of acetonitrile and 109 parts of deionised water weretransferred to a 1 l round bottom flask equipped with mechanicalstirrer, temperature sensor and pH probe. The reaction mixture wascooled to 0 to 2° C. using an ice bath. 19.81 parts of cyanuric chloride(C) were then gradually added to the reaction mixture. 35.28 parts of3-N,N-Diethylamino aniline (B) were dissolved in 50 parts ofacetonitrile and added dropwise to the reaction mixture. The pH wasmaintained at values of 4 to 4.5 using sodium hydroxide solution and thetemperature was maintained below 2° C. After 3 hours, the temperaturewas raised to room temperature and the pH was maintained at 5 to 5.5using sodium hydroxide solution. The reaction mixture was stirred untilcompletion. The reaction mixture was diluted with deionised water andthe resulting solid was filtered and washed neutral. Upon drying 47.26parts of solid (H) were obtained. The analytic data are consistent withthe assigned structure for product (H).

c) A reaction mixture comprising 10 parts of intermediate (H), 50 partsof acetonitrile, 2.26 parts of sodium bicarbonate dissolved in 3 partsof water and 2.71 parts of 2-mercapto ethanol (I) was heated to 80° C.until completion. After cooling to room temperature, the reactionmixture was diluted with deionised water. The pH of the reaction mixturewas adjusted to 6.5 to 7 using hydrochloric acid solution. The slurrywas stirred overnight and then filtered and washed neutral withdeionised water. Upon drying 10.94 parts of the product (J) as a darkgrey solid were obtained. The analytic data are consistent with theassigned structure for product (J).

d) 8.16 parts of 3-amino-4-methyl phenylsulfanilic acid (K) were takeninto 80 parts of deionised water. The pH of the mixture was adjusted to6.3 when a clear solution was obtained. The solution was cooled down to0 to 5° C. using an ice-salt mixture. 9.15 parts of 5N sodium nitritesolution were added dropwise into the reaction mixture, followed by fastaddition of 15.07 parts of 37% HCl to the reaction mixture. The reactionmixture was stirred for 2.5 hours at 0 to 5° C. and the resultingdiazonium salt was used for the following coupling step.

e) 10 parts of the coupler (J) and 0.36 parts of sulphamic acid weremixed with 50 ml of deionised water and 150 ml of acetonitrile. The pHof the resulting mixture was adjusted to pH 2.5 using 37% hydrochloricacid. The reaction mixture was cooled down to 0 to 5° C. using ice-saltmixture. The diazonium salt (L) was added dropwise to the couplersolution while maintaining the pH between 2.5 and 5.5 using sodiumhydroxide solution. The reaction mixture was stirred for 3 hrs and thereaction was completed. After distillation under reduced pressure the pHwas adjusted to 5 using hydrochloric acid. Upon addition of sodiumchloride, the resulting slurry was filtered and washed neutral. Upondrying 18.22 parts of the acid dye (1-1) were obtained. The analyticaldata is consistent with the assigned structure for the dye (1-1).

Through analogy, all the inventive dyes—and those in Table 1 inparticular—can be obtained by processes similar to those described abovein Example 1-1.

DYEING EXAMPLE 1

1 part of the dye, example 1-1 of this invention is dissolved in 2000parts of water and 1 part of levelling assistant (based on condensationproduct of a higher aliphatic amine and ethylene oxide) and 6 parts ofsodium acetate are added. The pH is then adjusted to 5 using acetic acid(80%). The dyebath is heated to 50° C. for 10 minutes and then enteredwith 100 parts of a woven polyamide-6 fabric. The temperature is raisedto 98° C. over the course of 50 minutes and then dyeing is carried outat this temperature for 60 minutes. This is followed by cooling to 60°C. and removal of the dyed material. The polyamide-6 fabric is washedwith hot and cold water, soaped and then spun dried. The scarlet dyeingsobtained have very good light and wet fastness and also good levelnessin the fibre.

DYEING EXAMPLE 2

1 part of the dye, example 1-1 of this invention is dissolved in 2000parts of water and 1 part of levelling assistant (based on condensationproduct of a higher aliphatic amine and ethylene oxide) and 6 parts ofsodium acetate are added. The pH is then adjusted to 5.5 using aceticacid (80%). The dyebath is heated to 50° C. for 10 minutes and thenentered with 100 parts of a woven polyamide-6,6 fabric. The temperatureis raised to 120° C. over the course of 50 minutes and then dyeing iscarried out at this temperature for 60 minutes. This is followed bycooling to 60° C. and removal of the dyed material. The polyamide-6,6fabric is washed with hot and cold water, soaped and then spun dried.The scarlet dyeings obtained have very good light and wet fastness andalso good levelness in the fibre.

DYEING EXAMPLE 3

100 parts of polyamide-6 material are padded with a 1000 parts 50° C.liquor solution that consists of 40 parts of the dye, example 1-1, 100parts of urea, 20 parts of a non ionic solubilizer based onbutyldiglycol, 20 parts of acetic acid to adjust the pH to 4.0, 10 partsof levelling assistant (based on ethoxylated aminopropyl fatty acidamide) and 810 parts of water. The material is rolled up and placed intoa steaming chamber at 85 to 98° C. for 3 to 6 hours. After fixation, thefabric is washed with hot and cold water, soaped and then spun dried.The scarlet dyeings obtained have very good light and wet fastness andalso good levelness in the fibre.

DYEING EXAMPLE 4

1 part of the dye, example 1-1 of this invention is dissolved in 2000parts of water and 5 parts of sodium sulphate, and 1 part of levellingassistant (based on condensation product of a higher aliphatic amine andethylene oxide) and 5 parts of sodium acetate are added. The pH is thenadjusted to 4.5 using acetic acid (80%). The dyebath is heated to 50° C.for 10 minutes and then entered with 100 parts of a woven wool fabric.

The temperature is raised to 100° C. over the course of 50 minutes andthen dyeing is carried out at this temperature for 60 minutes. This isfollowed by cooling to 90° C. and removal of the dyed material. The woolfabric is washed with hot and cold water, soaped and then spun anddried. The scarlet dyeings obtained have very good light and wetfastness and also good levelness in the fibre.

DYEING EXAMPLE 5

1 part of the dye, example 1-1 of this invention is dissolved in 1000parts of water and 7.5 parts of sodium sulphate, and 1 part of a wettingagent (anionic) are added. 100 parts of bleached cotton knitted fabricare added to this solution. The dye bath is then heated up to 98° C.with a gradient of 2° C./min then dyeing is carried out at thistemperature for 60 minutes. This is followed by cooling down to 80° C.At 80° C. the dyeing is continued for another 20 minutes. The dyedmaterial is then removed and is washed with hot and cold water, soapedand then spun and dried. The scarlet dyeings obtained have very goodlight and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 6

3 parts of the dye, example 1-1 of this invention dissolved in 82 partsof deionized water are added into the dyebath with 15 parts ofdiethylene glycol at 60° C. On cooling, a scarlet printing ink isobtained. The scarlet printing ink can be used for ink jet printing onpaper, polyamide or wool textiles.

DYEING EXAMPLE 7

4 parts of chemically bleached (pine wood) sulphite pulp is mixed upwith 100 parts of 55° C. water. 1 part of the dye 1a¹⁶¹ of thisinvention is dissolved in 100 parts of hot water. 80 parts of thissolution is given to the mixed-up pulp and mixed for 2 minutes. Afterthat the mixture is sized with resin size in a conventional manner andmixed for another 2 minutes. 55 parts of this solution are then dilutedwith 2000 parts of cold water and the paper is produced out of thissolution. The orange paper produced from the mixture has good wetfastnesses.

1.-13. (canceled)
 14. A dye of formula (1)

wherein independent from each other G is a rest of formula (i) or (ii)

R¹, R², R³ and R⁴ is hydrogen, (C₁-C₁₂)-alkyl, (C₂-C₆)-alkenyl,(C₃-C₈)-cycloalkyl or aryl-(C₁-C₁₂)-alkyl, with the alkyl chain beinglinear or branched, and optionally being interrupted by one or moreheteroatoms and/or substituted by one or more substituents selected fromthe group consisting of hydroxy, carboxy, SO₃M, halogen, cyano, nitro,acyl, trifluoromethyl, acyloxy, aryloyloxy and carbamoyl, R⁵ and R⁶ ishydrogen, (C1-C₁₂)-alkyl, substituted (C₁-C₁₂)-alkyl with thesubstituents being selected from the group consisting of hydroxy,carboxy, SO₃M, halogen, cyano, nitro, acyl, trifluoromethyl, acyloxy,aryloyloxy and carbamoyl, (C₃-Cg)-cycloalkyl, a group of formula (iii)

wherein R²⁶ and R²⁷ are identical or different and are hydrogen,(C₁-C₁₂)-alkyl, (C₁-C₁₂)-alkyl substituted by hydroxy, (C₁-C₁₂)-alkoxy,trifluoromethyl, cyano, nitro, halogen, —NHCO(C₁-C₆)-alkyl,—NHSO₂(C₁-C₆)-alkyl, CONH₂ or SO₂NH₂, R⁴¹ is hydrogen or (C₁-C₆)-alkyl,n is 0,1 or 2, p is 0 or 1 to 6, or (C₁-C₁₂)-alkyl, whereby the alkylchain can be interrupted by one or more heteroatoms, R⁷ and R⁸ areidentical or different and are hydrogen, (C₁-C₆)-alkyl or phenyl, R⁹ andR¹⁰ are identical or different and are hydrogen, (C₁-C₆)-alkyl,(C₁-C₆)-alkoxy, trifluoromethyl, hydroxy, cyano, nitro, halogen, —NHCHO,—NHCO(C₁-C₆)-alkyl, —NHCOaryl, —NHSO₂(C₁-C₆)-alkyl or —NHSO₂aryl, D₁ andD² is a rest of a phenyl-, naphthyl- or heterocyclic-derivative, whichcomprises at least one group —SO₃M, wherein M is hydrogen, an alkalimetal, ammonium, substituted or unsubstituted tetra(C₁-C₁₂)-alkylammonium or one equivalent of an alkali earth metal.
 15. The dyeaccording to claim 14, wherein independent from each other R¹ to R⁴ areidentical and are hydrogen, (C₁-C₄)-alkyl or (C₁-C₆)-alkyl substitutedby hydroxyl, cyano or alkenyl, R³ and R⁶ are identical and are hydrogen,(C₁-C₆)-alkyl, (C₁-C₆)-alkyl substituted by hydroxy, (C₃-C₈)-cycloalkylor (C₁-C₆)-alkyl substituted by —SO₃M or a group of formula (iii) asdefined in claim 14, wherein each R²⁶ and R²⁷ independent from eachother is hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkyl substituted by hydroxy,(C₁-C₆)-alkoxy, trifluoromethyl, hydroxy, cyano, halogen, n is 0 or 1, pis 0 or 1 to 4, R⁷ and R⁸ are identical and are hydrogen, methyl orethyl and R⁹ and R¹⁰ are identical and are hydrogen, methyl, ethyl,halogen, trifluoromethyl, methoxy or ethoxy.
 16. The dye according toclaim 14, having formula (1a), (1a¹), (1a²) or (1a³)

wherein R^(5a) and R ^(6a) are hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkylsubstituted by hydroxy, (C₃-C₈)-cycloalkyl or (C₁-C₆)-alkyl substitutedby SO₃M, R^(9a) and R^(10a) are identical and are hydrogen or methoxy,each of R^(26a), R^(27a), R^(26b) and R^(27b) is hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, trifluoromethyl, cyano, nitro or halogen,R^(43a) and R^(43b) is hydrogen or (C₁-C₄) alkyl, s is 0 or 1 to 6 andD¹ and D² are as defined in claim
 14. 17. The dye according to claim 14,in which independent from each other D¹ and D² is selected from thegroup consisting of groups of formula (I) to (XIV):

wherein R¹¹ and R³⁰ independent of each other is hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, trifluoromethyl, cyano, nitro, NHC(O)R³¹,CONH₂, S(O)₂R³² or halogen, R³¹ and R³² is hydrogen, (C₁-C₄)-alkyl or(C₁-C₄)-alkyl substituted by hydroxyl, M is hydrogen, an alkali metal,ammonium or one equivalent of an alkali earth metal,

wherein R¹² is hydrogen or (C₁-C₄)-alkyl, n is 0 or 1 and M is definedas given above,

wherein R¹³ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, cyano, nitro,CONH₂ or halogen and M is defined as given above,

wherein R¹⁴ is hydrogen, cyano, CONH₂, C(O)R³³ or COOR³⁴, R³³ ishydrogen or (C₁-C₄)-alkyl, R³⁴ is hydrogen or (C₁-C₄)-alkyl, R¹⁵ ishydrogen, —CHO or a group of formula (a) or (c)

wherein R¹⁶, R³⁵ and R³⁶ independent of each other is hydrogen, halogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, SO₃M or —CONH₂, m is 0 or 1 and M isdefined as given above,

wherein M is defined as given above,

wherein R¹⁷ is —SO₃M, —CHO, —CH═C(CN)₂, a group of formula (a) asdefined above or a group of formula (b) or (d)

wherein R³⁷, R³⁸ and R³⁹ independent of each other is hydrogen, halogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, SO₃M or —CONH₂, R¹⁸ is —SO₃M,(C₁-C₄)-alkyl, sulfophenyl (C₁-C₄)-alkylamino, (C₁-C₁₂)-alkylamino,(C₅-C₆)-cycloalkylamino, morpholino or piperidino and M is defined asgiven above,

wherein R¹⁹ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro,NHC(O)R⁴⁰, NHSO₂R⁴⁷ or halogen, R⁴⁰ is hydrogen or (C₁-C₆) alkyl, R⁴⁷ is(C₁-C₆)-alkyl,

wherein R²⁰ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, cyano, nitro,CONH₂ or halogen,

wherein R²¹ is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, cyano,nitro or CONH2 and E is sulphur or oxygen,

wherein R²² and R²³ independent of each other is hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, cyano or CONH₂ and U ismethylene or C═O,

wherein R²⁴ and R²⁵ independent of each other is hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, cyano, nitro, trifluoromethyl orCONH₂,

wherein R⁴⁴ and R⁴⁵ independent of each other is hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, cyano, nitro, trifluoromethyl,CONH₂, or SO₃M.

wherein R⁴⁶ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, cyano,nitro, trifluoromethyl, CONH₂ or SO₃M and

wherein R⁴⁸ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro,NHC(O)R⁴⁹, NHSO₂R⁵⁰ or halogen, R⁴⁹ is hydrogen or (C₁-C₆)-alkyl, R⁵⁰ is(C₁-C₆)-alkyl; and M is defined as given above.
 18. The dye according toclaim 17, wherein D¹ and D² are identical.
 19. A chemical compositioncomprising one or more dye(s) according to claim
 14. 20. A chemicalcomposition consisting of two or more dyes according to claim
 14. 21. Anaqueous solution for dying comprising one or more chemical compoundsaccording to claim
 14. 22. Process for the production of the dyeaccording to claim 14, comprising a) diazotizating compounds of formulae(2) and (3)D¹-NH₂   (2)D²-NH₂   (3), wherein D¹ and D² are defined as given in claim 14, b)reacting the products obtained in step a) with a compound of formula (4)

wherein R¹ to R¹⁰ and G are defined as given in claim
 14. 23. A processfor dyeing or printing carboxamido- and/or hydroxyl-containing material,comprising contacting the carboxamido- and/or hydroxyl-containingmaterial with the dye according to claim
 14. 24. An ink for digitaltextile printing comprising the dye according to claim
 14. 25. A processfor dying a fiber or blend which comprises contacting the fiber or blendof fibers with the dye according to claim
 14. 26. The process accordingto claim 25, wherein the fiber is selected from the group consisting of:synthetic fiber materials; nylon materials; nylon-6; nylon-6,6; aramidfibres; vegetable fibres; seed fibres; cotton; organic cotton; kapok;coir from coconut husk; bast fibers; flax; hemp; jute; kenaf; ramie;rattan; leaf fibres; sisal; henequen; banana; stalk fibres; bamboo;fibres from animals; wool; organic wool; silk; cashmere wool; alpacafiber; mohair; Angora fibre; fur and leather materials; manufactured,regenerated and recycled fibres; cellulosic fibres; paper fibres;cellulosic regenerated fibres; viscose rayon fibres; acetate andtriacetate fibers; Lyocell fibers and mixtures thereof.
 27. A fiber orblends comprising one or more dye(s) according to claim 14 either inchemically and/or physically bound form.
 28. The fiber or blends asclaimed in claim 27, wherein the fiber is selected from the groupconsisting of: synthetic fiber materials; nylon materials; nylon-6;nylon-6,6; aramid fibres; vegetable fibres; seed fibres; cotton; organiccotton; kapok; coir from coconut husk; bast fibers; flax; hemp; jute;kenaf; ramie; rattan; leaf fibres; sisal; henequen; banana; stalkfibres; bamboo; fibres from animals; wool; organic wool; silk; cashmerewool; alpaca fiber; mohair; Angora fibre; fur and leather materials;manufactured, regenerated and recycled fibres; cellulosic fibres; paperfibres; cellulosic regenerated fibres; viscose rayon fibres; acetate andtriacetate fibers; Lyocell fibers and mixtures thereof.